1. Field of the Invention
The present invention relates to a method for producing an ester that includes a reaction in the presence of a Lewis acid catalyst and a phosphorus-containing reducing agent, and an ester, obtained by the production method. The present invention also relates to ester lubricating base stocks for grease, refrigerating machine oil and automotive engine oil and compositions containing the base stock.
2. Description of the Related Art
Esters are used in a wide range of fields such as cosmetics, pharmaceutical preparations, foods, electronic equipment, printing, and lubrication, etc. In recent years, with technological development in these fields using esters, each field requires esters with suitable qualities. For example, for esters used for grease, durability and anti-evaporation properties at high temperatures are required. For esters used for engine oil, long life and good thermal and oxidative stability are required. For esters used for refrigerating machine oils, high electric insulation properties and heat resistance are required, and it is also required that contaminants or conductive impurities are hardly contained, the acid value and hydroxyl value of the esters are low, and the hydrolytic stability and heat stability at high temperatures of the esters are excellent.
Esters can be obtained by a reaction between a carboxylic acid and an alcohol. In general, the reaction is carried out with an excessive amount of the carboxylic acid in order to obtain esters having a low hydroxyl value. In this esterification reaction, a Brxcfx86nsted acid such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, or naphthalenesulfonic acid is commonly used as a catalyst. In the esterification reaction using such a Brxcfx86nsted acid, byproducts tend to be produced. The produced byproducts and the remaining catalyst are removed by purification by means of neutralization with an alkali, adsorption with an adsorbent, steaming, etc., which can be performed alone or in combination. However, it is difficult to sufficiently remove the byproducts and the remaining catalyst, and the remaining byproducts and catalyst are factors that may deteriorate the thermal and oxidative stability of the esters. Thus, there is no ester that satisfies the various requirements.
Japanese Laid-Open Patent Publication Nos. 54-91589 and 54-132502 describe a method for performing esterification in the presence of an acid catalyst such as a Brxc3x8nsted acid and an ion exchange resin and phosphorous acid, hypophosphorous acid or salts thereof. Japanese Patent Publication No. 7-45437 describes a method for producing esters that includes a process of ester exchange in the presence of a mono-organic tin compound. Although these methods have some effects in that less colored esters can be obtained, the long-time thermal and oxidative stability is still insufficient.
In another example, less colored polyester is produced by adding a stabilizer containing a phosphorus-containing compound, a phenol-containing compound, a thioether-containing compound, an amine compound or the like, as disclosed in Japanese Laid-Open Patent Publication No. 7-309937. However, it is difficult to remove these stabilizers from the reaction product, and the stabilizer that remains in ester acts as an accelerator of deterioration of the ester so that sludge may be produced or discoloring may be caused when used at a high temperature for a long time.
Examples of Japanese Laid-Open Patent Publication No. 2000-508691 include a method using dibutyltin oxide as a catalyst for esterification. However, the ester obtained by this method is colored at high temperatures, and the ester has a high acid value, and, thus, the thermal and oxidative stability of the ester is insufficient. Furthermore, for all the engine oils described in PCT Publication No. WO 97/008277, esters produced in the absence of a catalyst are used as the base stock. The method described therein requires esterification reaction at a high temperature for a long time in the process of producing the esters, so that the esters are thermally deteriorated significantly during the reaction. Therefore, the heat resistance of the ester base stock is not sufficient, and there are problems with regard to the long-term stability.
Base catalysts are also known as catalysts for esterification. For example, N,Nxe2x80x2-dicyclohexylcarbodiimide-4-(N,N-dimethylamino) pyridine, triphenyl phosphine-2,2xe2x80x2-dipyridyl sulfide or the like is used. However, when the base catalyst is used, the reaction mixture is colored blackish brown, and thus, high quality esters cannot be obtained.
As described above, there is no method for producing high quality esters that satisfies the requirements of various fields.
The method for producing an ester of the present invention includes reacting an alcohol with a carboxylic acid and comprises: reacting the alcohol with the carboxylic acid in a presence of a Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and a phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid, and separating a resultant ester.
In a preferred embodiment, the Lewis acid catalyst is at least one selected from the group consisting of titanium-containing Lewis acid catalysts, tin-containing Lewis acid catalysts, antimony-containing Lewis acid catalysts, germanium-containing Lewis acid catalysts, and zirconium-containing Lewis acid catalysts.
In a preferred embodiment, the alcohol is a neopentyl polyol having 2 to 6 hydroxyl groups, and the carboxylic acid is a monocarboxylic acid having 5 to 10 carbon atoms.
In a preferred embodiment, the alcohol is a neopentyl polyol having 2 to 4 hydroxyl groups, and the carboxylic acid is a monocarboxylic acid having 5 to 12 carbon atoms.
The ester of the present invention is obtained by a process comprising: reacting an alcohol with a carboxylic acid in a presence of a Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and a phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid, and separating a resultant ester, wherein the acid catalyst and the reducing agent are substantially removed from the resultant ester.
The ester lubricating base stock for grease of the present invention is obtained by a method comprising: reacting a neopentyl polyol having 2 to 6 hydroxyl groups with a monocarboxylic acid having 5 to 10 carbon atoms in the presence of a Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and a phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid, and separating a resultant ester, wherein the acid catalyst and the reducing agent are substantially removed from the resultant ester.
The ester lubricating base stock for refrigerating machine oil of the present invention is obtained by a process comprising: reacting a neopentyl polyol having 2 to 6 hydroxyl groups with a monocarboxylic acid having 5 to 10 carbon atoms in a presence of a Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and a phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid, and separating a resultant ester, wherein the acid catalyst and the reducing agent are substantially removed from the resultant ester.
The ester lubricating base stock for automotive engine oil obtained by a process comprising: reacting a neopentyl polyol having 2 to 4 hydroxyl groups with a monocarboxylic acid having 5 to 12 carbon atoms in a presence of a Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and a phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid, and separating a resultant ester, wherein the acid catalyst and the reducing agent are substantially removed from the resultant ester.
In a preferred embodiment, the grease composition comprises the above-mentioned ester lubricating base stock for grease, a thickener, and an antioxidant, and wherein the ester lubricating base stock for grease is contained in a ratio of 10 to 90% by weight.
In a preferred embodiment, the working fluid composition for refrigerating machine oil comprises the above-mentioned ester lubricating base stock for refrigerating machine oil and a hydrofluorocarbon in a weight ratio of 10:90 to 90:10.
The composition for engine oil of the present invention comprises the above-mentioned ester lubricating base stock for automotive engine oil, an anti-wear additive, and an antioxidant, and wherein the ester lubricating base stock for automotive engine oil is contained in a ratio of 5 to 95% by weight.
Thus, the present invention described herein makes possible the advantages of providing a method for producing high quality esters, especially esters having excellent thermal and oxidative stability, and esters obtained by this method; and providing ester lubricating base stocks for grease, automotive engine oil, and refrigerating machine oil that contain the esters and that can be used for a long period of time even under severe use conditions of high speed and high load of recent machines; and compositions containing these base stocks.
Carboxylic Acid
Examples of the carboxylic acid used in the present invention include monocarboxylic acids and polycarboxylic acids. These carboxylic acids can be either saturated or unsaturated carboxylic acids and can be either linear or branched. Preferably, saturated and linear or branched carboxylic acids are used.
Examples of the monocarboxylic acids include valeric acid, isovaleric acid, caproic acid, 2-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, isoheptanoic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, neononanoic acid, capric acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid, linolenic acid, arachic acid, erucic acid, behenic acid, lignoceric acid, cerotic acid, montanoic acid, melissic acid, and the like.
Examples of the polycarboxylic acids include succinic acid, glutanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, carboxyoctadecanoic acid, carboxymethyloctadecanoic acid, docosanedioic acid, dimer acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, trimellitic acid, pyromellitic acid, and the like.
These carboxylic acids can be used alone or in combination.
Alcohol
Examples of the alcohol used in the present invention include monohydric alcohols, polyhydric alcohols and ether compounds that can be obtained by an addition reaction of an alkylene oxide with the alcohol.
Examples of the monohydric alcohols include pentanol, isopentanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonanol, 3,5,5-trimethylhexanol, isononanol, decanol, isodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, nonacosanol, melissyl alcohol and the like.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, polyalkylene glycols, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, spiroglycol, 1,4-phenylene glycol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,3,6-hexanetetraol, 2-methyl-1,2,4-butanetriol, erythrite, arabitol, sorbitol, mannitol, sorbitan, glycerine, 2-methylpropanetriol, neopentylglycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, trimethylolethane, triethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-trihydroxymethylbenzene and the like.
Examples of the alkylene oxide that can be used for the addition reaction include ethylene oxide, propylene oxide, butylene oxide, and the like.
These alcohols can be used alone or in combination.
Lewis Acid Catalyst
Examples of the Lewis acid catalyst used in the present invention include titanium-containing Lewis acid catalysts, tin-containing Lewis acid catalysts, antimony-containing Lewis acid catalysts, zinc-containing Lewis acid catalysts, germanium-containing Lewis acid catalysts, zirconium-containing Lewis acid catalysts, and hafnium-containing Lewis acid catalysts.
Examples of the titanium-containing Lewis acid catalysts include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraoctoxide, titanium ethylacetoacetate, octylene glycol titanate, and the like.
Examples of the tin-containing Lewis acid catalysts include monoalkyl tin esters, dialkyl tin esters, monoalkyl tin oxides, dialkyl tin oxides, and the like. As alkyl groups contained in the compounds used as the tin-containing catalysts, linear or branched alkyls having 1 to 12 carbon atoms are preferable. Specific examples of the tin-containing catalyst include monobutyltin mono(2-ethylhexanoate), monobutyltin tris(2-ethylhexanoate), dibutyltin bis(2-ethylhexanoate), stannous 2-ethylhexanoate, dibutyltin diacetate, monobutyltin oxide, dibutyltin oxide, and the like.
Examples of the antimony-containing Lewis acid catalysts include antimony triethoxide, antimony tributoxide, antimony trioxide, and the like.
Examples of the zinc-containing Lewis acid catalysts include zinc chloride, zinc acetate, and zinc carbonate.
Examples of the germanium-containing Lewis acid catalysts include germanium selenide, germanium dioxide, germanium tetrachloride, germanium tetra-n-butoxide, and the like.
Examples of the zirconium-containing Lewis acid catalysts include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium oxide, zirconium tungstate, zirconium tetra-2-ethylhectoxide, and the like.
Examples of the hafnium-containing Lewis acid catalysts include hafnium tetramethoxide, hafnium tetraethoxide, hafnium tetra-t-butoxide, hafnium tetra-2-ethylhexyloxide, hafnium oxychloride, hafnium tetrachloride, hafnium oxide, and the like.
Among these Lewis acid catalysts, titanium-containing catalysts, tin-containing catalysts, zirconium-containing catalysts, antimony-containing catalysts and germanium-containing catalysts are preferable in view of reactivity. More specifically, the following compounds are preferable: titanium tetraisopropoxide, titanium tetra-n-butoxide, monobutyltin mono(2-ethylhexanoate), monobutyltin tris(2-ethylhexanoate), stannous 2-ethylhexanoate, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, antimony triethoxide, antimony tributoxide, germanium tetra-n-butoxide and germanium tetrachloride.
The Lewis acid catalyst is used in a ratio of 0.00001 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid subjected to esterification reaction. When the Lewis acid catalyst is used in less than 0.00001 mol, not only the reaction requires a long time, but also the productivity is reduced. When the Lewis acid catalyst is used in an amount of more than 0.005 mol, the effect is not improved in proportion to the amount used, and the production cost is increased. Furthermore, this makes it difficult to remove the catalyst from the ester, so that the thermal and oxidative stability of the ester may be deteriorated. When the Lewis acid catalyst is used in an amount in the above range, the amount of the remaining metal derived from the Lewis acid catalyst in the resultant ester is substantially not more than the measurement limit.
Phosphorus-Containing Reducing Agent
Examples of the phosphorus-containing reducing agent used in the present invention include phosphorous acid, hypophosphorous acid and salts thereof. Among these, salts of phosphorous acid and salts of hypophosphorous acids are used preferably. Examples of salts of phosphorous acid and salts of hypophosphorous acid include sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, barium salts, ammonium salts, and the like. Among these, sodium salts are used preferably.
The phosphorus-containing reducing agent is used in a ratio of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid subjected to esterification reaction. A ratio of 0.001 to 0.003 mol is preferable. When it is less than 0.0003 mol, the effect of improving the thermal and oxidative stability of the resultant ester is insufficient. When the phosphorus-containing reducing agent is used in an amount of more than 0.005 mol, the effect is not improved in proportion to the amount used. Furthermore, this makes it difficult to remove it from the ester, so that the thermal and oxidative stability of the ester may be deteriorated. When the phosphorus-containing reducing agent is used in an amount in the above range, the amount of the remaining phosphorus in the produced ester is substantially not more than the measurement limit.
Method for Producing Ester
Next, a method for producing esters of the present invention will be described. In esterification reaction, usually, the amounts of the carboxylic acid and the alcohol that are used are such that the amount of carboxyl groups of the carboxylic acid is 1.0 to 1.5 equivalents with respect to one equivalent of hydroxyl groups of the alcohol. In order to obtain an ester having a low hydroxyl value, it is necessary to perform an esterification reaction in the presence of excessive carboxylic acid. The equivalent ratio is 1.0 equivalent or more. When it exceeds 1.5 equivalents, removal of the excessive carboxylic acid is required after the reaction, which reduces the productivity.
In the method of the present invention, the carboxylic acid and the alcohol that have been adjusted to a suitable ratio are subjected to esterification reaction in the presence of suitable amounts of the Lewis acid and the phosphorus-containing reducing agent. The reaction is performed usually at 120 to 260xc2x0 C. for 3 to 15 hours. After the reaction is completed, purification is performed by a method that is generally used by those skilled in the art, such as neutralization with an alkali, adsorption with an adsorbent, steaming, distillation or the like, which can be performed alone or in combination, and thus the ester of the present invention can be obtained. Among these methods for purification, a combination of neutralization with an alkali and adsorption with an adsorbent is preferable in view of the thermal and oxidative stability of the ester.
Examples of the alkali used for neutralization include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, potassium carbonate, and sodium hydrogencarbonate; and ammonium salts such as ammonium carbonate. Among these, sodium hydroxide and potassium hydroxide are preferable. The amount of alkali used for neutralization is 1 to 2 equivalents with respect to 1 equivalent of the acid value of the ester, and the alkali is used in the form of an alkali aqueous solution having a concentration of 5 to 20 wt %.
Examples of the adsorbent include activated clay, acid white clay, activated carbon, zeolite, activated alumina, diatomaceous earth, silicon dioxide, aluminum oxide, magnesium oxide, and silica-alumina-containing synthetic adsorbents. Among these, activated clay and silica-alumina-containing synthetic adsorbents are preferable. A preferable amount of an adsorbent used is 0.1 to 5.0 parts by weight with respect to one part by weight of the produced ester.
In a conventional ester that is produced by the use of Brxcfx86nsted acids or the like as the catalyst, byproducts and the catalyst cannot be removed completely. On the other hand, in the present invention, an ester from which byproducts, the catalyst, and the reducing agent are almost completely removed can be produced, partly because the Lewis acid catalyst and the phosphorus-containing reducing agent are used in low concentrations. The concentrations of metal derived from the Lewis acid catalyst and phosphorus derived from the reducing agent in the produced ester are not more than the detection limit, and they are substantially not contained in the ester. Esters that have such a property have excellent thermal and oxidative stability and are not colored for a long time, as shown in the examples below.
The esters obtained by the method of the present invention are used for various applications such as ester lubricating base stock for grease, ester lubricating base stock for refrigerating machine oil, or ester lubricating base stock for automotive engine oil.
Ester Lubricating Base Stock for Grease and Grease Compositions Containing the Base Stock
Esters used as ester lubricating base stocks for grease are esters obtained from a neopentyl polyol having 2 to 6 hydroxyl groups and a monocarboxylic acid having 5 to 10 carbon atoms, and are produced in the presence of the Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and the phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid. The catalyst and the reducing agent are removed to the measurement limit or less in the process of purification and are substantially not contained in the ester. The thus obtained ester has the advantages of having excellent non-coloring properties and excellent thermal and oxidative stability, being hardly volatized (the weight decreasing rate is small) even if it is used for a long time, being not colored (the non-coloring properties are excellent), and producing little sludge compared to conventional esters.
The neopentyl polyol having 2 to 6 hydroxyl groups is used preferably because it provides the produced ester with excellent heat resistance. Preferable examples of the neopentyl polyol having 2 to 6 hydroxyl groups include neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Among these, trimethylolpropane, pentaerythritol, and dipentaerythritol are more preferable because of the anti-evaporation properties of the obtained ester at high temperatures. In view of long life of grease, pentaerythritol and dipentaerythritol are particularly preferable.
As mentioned above, a monocarboxylic acid having 5 to 10 carbon atoms is preferably used. It is more preferable that branched monocarboxylic acid is contained in the monocarboxylic acids because it provides the resultant ester with excellent low temperature fluidity. It is preferable that the branched monocarboxylic acid is contained in an amount of 25 wt % or more based on the total amount of the monocarboxylic acid. On the other hand, when the ratio of the branched monocarboxylic acid is too large, the anti-evaporation properties at high temperatures may be deteriorated, so that it is preferable that the ratio of the branched monocarboxylic acid is 75 wt % or less. Therefore, it is preferable that the branched monocarboxylic acid is contained in the monocarboxylic acid in a ratio of 25 to 75 wt %. As the branched monocarboxylic acid having 5 to 10 carbon atoms, branched monocarboxylic acid having 7 or more carbon atoms is preferable in view of the anti-evaporation properties, and branched monocarboxylic acid having 9 or less carbon atoms is preferable in view of the low temperature fluidity. The branched carboxylic acid is preferably xcex1- or xcex2-branched carboxylic acid in view of the heat resistance and the hydrolytic stability, and xcex1-branched carboxylic acid is more preferable. More specifically, the following compounds can be used preferably: 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, neononanoic acid, and the like.
It is preferable that the acid value of the ester is 0.1 mgKOH/g or less in view of the heat resistance and the hydrolytic stability, and more preferably 0.05 mgKOH/g or less. It is preferable that the hydroxyl value of the ester is 10 mgKOH/g or less in view of the anti-evaporation properties at high temperatures and the low temperature fluidity. When the hydroxyl value exceeds 10 mgKOH/g, the thermal and oxidative stability at high temperature is poor, and a sealing material is expanded when sealing is performed with grease containing the ester.
The grease composition of the present invention comprises a base stock that is the ester mentioned above, a thickener, an antioxidant, and if necessary, additives that are generally used, such as an extreme pressure additive, an anticorrosive additive, a defoaming agent, an antiemulsifier, and the like.
Examples of the thickener include complex soaps such as lithium complex salts, calcium complex salts, aluminum complex salts, and the like; alkaline metal salts or alkaline earth metal salts such as calcium salts, sodium salts, lithium salts, and the like; and urea, terephthalamide, and the like. Among these, lithium complex salts, lithium salts and urea are preferable in view of the heat resistance.
Examples of the antioxidant include phenol antioxidants such as 2,6-di-t-butyl-4-methylphenol, 4,4xe2x80x2-methyl bis(2,6-di-t-butyl-4-methylphenol), and the like; amine antioxidants such as p,pxe2x80x2-dioctyl phenylamine, monooctyl diphenylamine, phenothiazine, 3,7-dioctyl phenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkyiphenyl-1-naphthylamine, alkylphenyl-2-naphthylamine, and the like; zinc dialkyl dithiophosphate, zinc diallyl dithiophosphate, and the like. These antioxidants can be used alone or in combination of two or more.
Ester Lubricating Base Stock for Refrigerating Machine Oil and Working Fluid Composition for Refrigerating Machine Oil Containing the Base Stock
Esters used as ester lubricating base stocks for refrigerating machine oil are esters obtained from a neopentyl polyol having 2 to 6 hydroxyl groups and a monocarboxylic acid having 5 to 10 carbon atoms, as in the case of the ester used as ester lubricating base stocks for grease. The esters are produced in the presence of the Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and the phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid. The catalyst and the reducing agent are removed to the measurement limit or less in the process of purification and are substantially not contained in the ester. The thus obtained ester has the advantages of having excellent non-coloring properties and excellent thermal and oxidative stability, being not substantially changed in its acid value in the sealed tube tests (described below), and being not colored for a long period of time (i.e., the non-coloring properties are excellent), compared to conventional esters.
The neopentyl polyol having 2 to 6 hydroxyl groups is used preferably because the resultant ester can be provided with excellent heat resistance. Preferable examples of the neopentyl polyol having 2 to 6 hydroxyl groups include neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like.
As mentioned above, a monocarboxylic acid having 5 to 10 carbon atoms is preferably used, and a monocarboxylic acid having 5 to 9 carbon atoms is more preferable. It is preferable that branched monocarboxylic acid is contained in the monocarboxylic acid having 5 to 9 carbon atoms because the resultant ester can be provided with excellent low temperature fluidity and miscibility and solubility with hydrofluorocarbon. It is preferable that the branched monocarboxylic acid is contained in an amount of 50 wt % or more based on the total amount of the monocarboxylic acid, more preferably 60 wt % or more, and even more preferably 70 wt % or more. The branched carboxylic acid is preferably xcex1- or xcex2-branched carboxylic acid in view of the heat resistance and the hydrolytic stability of the resultant ester, and xcex1-branched carboxylic acid is more preferable.
It is preferable that the acid value of the ester used as ester lubricating base stock for refrigerating machine oil is 0.05 mgKOH/g or less, and more preferably 0.01 mgKOH/g or less in view of the heat resistance and the hydrolytic stability. It is preferable that the hydroxyl value is 5 mgKOH/g or less, and more preferably 3 mgKOH/g or less in view of the compatibility with sealing material, the heat resistance and the hydrolytic stability. When the ester of the present invention is used as a base stock for refrigerating machine oil, an increase of the acid value and an increase in color number can be prevented in the sealed tube test (see the examples below).
The working fluid composition for refrigerating machine of the present invention comprises a base stock that is the ester mentioned above, a hydrofluorocarbon, and if necessary, additives that are commonly used by those skilled in the art, such as an antioxidant, an extreme pressure additive, a metal deactivator, a foaming agent, and the like.
In the above composition, when the content ratio of the hydrofluorocarbon is too high, the viscosity of the working fluid composition for refrigerating machine oil is reduced, which may cause poor lubrication. Therefore, the content ratio of the hydrofluorocarbon is preferably 90 wt % or less, more preferably 80 wt % or less. On the other hand, when the content ratio of the hydrofluorocarbon is too low, the refrigerating efficiency may be reduced, so that it is preferable that the content ratio of the hydrofluorocarbon is 10 wt % or more. Therefore, in view of the lubricity and the refrigerating efficiency, the content ratio of the ester lubricating base stock for refrigerating machine oil (i.e., the ester) to the hydrofluorocarbon is preferably 10:90 to 90:10 (weight ratio), more preferably 20:80 to 80:20 (weight ratio). Therefore, in view of the lubricity and the refrigerating efficiency, the content ratio of the ester lubricating base stock for refrigerating machine oil (i.e., the ester) to the hydrofluorocarbon is preferably 10:90 to 90:10 (weight ratio), more preferably 20:80 to 90:10 (weight ratio).
As the hydrofluorocarbon, 1,1,1,2-tetrafluoroethane (HFC134a), pentafluoroethane (HFC125), difluoromethane (HFC32) and the like are preferable. These can be used alone or in combination.
Ester Lubricating Base Stock for Automotive Engine Oil and Composition for Engine Oil Containing the Base Stock
Esters used as ester lubricating base stocks for automotive engine oil are esters of a neopentyl polyol having 2 to 4 hydroxyl groups and a monocarboxylic acid having 5 to 12 carbon atoms. The esters are produced in the presence of the Lewis acid catalyst in an amount of 0.00001 to 0.005 mol and the phosphorus-containing reducing agent in an amount of 0.0003 to 0.005 mol with respect to one mol of carboxyl groups of the carboxylic acid. The catalyst and the reducing agent are removed to the measurement limit or less in the process of purification and are substantially not contained in the ester. The thus obtained ester is substantially free from the catalyst and the reducing agent and has the advantages of having excellent non-coloring properties and excellent thermal and oxidative stability, and increasing the stability in the rotary bomb oxidation test (described later) by 10% or more, preferably 20% or more, and more preferably 30% or more.
As the neopentyl polyol having 2 to 4 hydroxyl groups, neopentylglycol, trimethylolpropane, pentaerythritol or the like can be used preferably.
A monocarboxylic acid having 5 to 12 carbon atoms is used preferably because it provides the resultant ester with excellent lubricity and excellent heat resistance. It is preferable that linear carboxylic acid is contained in the monocarboxylic acids in view of the temperature-viscosity characteristics and the lubricity of the resultant ester. It is preferable that the linear carboxylic acid is contained in an amount of 40 wt % or more based on the total amount of the monocarboxylic acids, more preferably 50 wt % or more, and even more preferably 60 wt % or more. When the branched carboxylic acid is used, the branched carboxylic acid is preferably xcex1- or xcex2-branched carboxylic acid in view of the heat resistance and the hydrolytic stability of the resultant ester, and xcex1-branched carboxylic acid is more preferable.
It is preferable that the kinematic viscosity of the ester used as ester lubricating base stock for automotive engine oil at 40xc2x0 C. is 8 to 50 mm2/s, and more preferably 10 to 40 mm2/s. When the kinematic viscosity is less than 8 mm2/s, the volatized amount of the ester at high temperatures is large, and the lubricity is deteriorated. A kinematic viscosity exceeding 50 mm2/s is not preferable because the power loss due to resistance caused by a high viscosity is too large. The hydroxyl value of the ester is preferably 5 mgKOH/g or less, more preferably 3 mgKOH/g or less. When it exceeds 5 mgKOH/g, the oxidative stability of the ester at high temperatures is poor and the detergency is insufficient.
The composition for automotive engine oil of the present invention comprises a base stock that is the ester mentioned above, an antioxidant, and if necessary, other synthetic lubricants and mineral oils, and additives that are commonly used, such as a detergent-dispersant, a viscosity index improver, an anti-wear additive, an extreme pressure additive, an oiliness agent, an anticorrosive additive, a defoaming agent, and the like.
Examples of the anti-oxidant include phenol antioxidants such as 2,6-di-t-butyl-4-methylphenol, 4,4xe2x80x2-methyl bis(2,6-di-t-butyl-4-methylphenol), and the like; amine antioxidants such as p,pxe2x80x2-dioctyl phenylamine, monooctyl diphenylamine, phenothiazine, 3,7-dioctyl phenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthylamine, alkylphenyl-2-naphthylamine, and the like; and zinc dialkyl dithiophosphate, zinc diallyl dithiophosphate, and the like. These antioxidants can be used alone or in combination of two or more.
Examples of the synthetic lubricant and mineral oils include poly-xcex1-olefins, high viscosity index semisynthetic oils, polyalkylene glycols, alkyl benzenes, naphthenic mineral oils, paraffin mineral oils, aromatic mineral oils, polybutene, and the like. Among these, poly-xcex1-olefins and high viscosity index semisynthetic oils are preferable because of good compatibility with sealing material and good temperature-viscosity characteristics. Examples of the anti-wear additive include zinc dithiophosphate, zinc dithiocarbamate, dialkyl polysulfides, triallyl phosphates, trialkyl phosphates, and the like. These additives can be used alone or in combination of two or more.
In this specification, although the characteristics of esters suitable for each application are described, some applications may use a common ester. In this case, the ester used for some applications has the same characteristics as for other applications.